Cycloolefin copolymer, and method for preparing and use thereof

Abstract

The application provides a cyclic olefin copolymer and a preparation method and application thereof, and belongs to the technical field of high polymer materials.The structure of the cyclic olefin copolymer is shown in formula I, and the polymerization monomers of the cyclic olefin copolymer include alpha-olefins, a cyclic olefin monomer with the structure shown in formula II and a cyclic olefin monomer with the structure shown in formula III.The chromophore is connected to the polymer through a chemical bond to obtain an intrinsic polymer-based long afterglow material, the problems of low solubility and uneven dispersion of the luminescent group in the polymer can be solved, phase separation is avoided, the polymer-based long afterglow material has more stable phosphorescent performance and optical performance, the cyclic olefin copolymer is more stable, has more optical performance and is easier to process, and can meet the use requirements of the current market.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and relates to a cycloolefin copolymer and a preparation method and application thereof. BACKGROUND

[0002] Cycloolefin copolymer (COC) refers to a polyolefin material containing a cyclic structure in the main chain, which is generally prepared by addition copolymerization of a cycloolefin and an alpha-olefin (usually ethylene). The cycloolefin polymer and the cycloolefin copolymer have good optical properties, low birefringence, extremely low dielectric constant, excellent heat resistance, chemical resistance, melt flowability and dimensional stability, good moisture barrier property and low water absorption, and are widely used in fields such as optical lenses, optical semiconductors and medical products.

[0003] Persistent luminescent materials are a class of functional materials that can emit light for a period of time after excitation stops. This class of materials stores energy after absorbing light or radiation, and then produces long-time luminescence (persistent luminescence) in a slow release manner, and has wide applications in the fields of biomedical and health such as biological imaging, endoscopic navigation, energy and environment such as environmental sensing, military and defense, and emerging intelligent materials.

[0004] Common persistent luminescent materials include sulfide, alkaline earth aluminate, silicate and titanate systems, but the preparation of such inorganic persistent luminescent materials requires the use of a large amount of rare earth elements and rare elements, resulting in an increase in cost, and is easily affected by external environment such as ultraviolet light and moisture, leading to a decrease in luminescent performance, and a series of disadvantages such as a large pollution to the environment due to the presence of heavy metal elements and radioactive elements. The cycloolefin copolymer has excellent heat resistance, high transparency, chemical corrosion resistance, low moisture absorption, good dielectric performance and dimensional stability, and is a good persistent luminescent material matrix. It can overcome the disadvantage that the PVA-based persistent luminescent material is easily affected by environmental factors to cause a large decrease in performance, and is more environmentally friendly and less expensive than inorganic persistent luminescent materials.

[0005] The inorganic persistent luminescent materials obtained by the prior art have high rigidity and brittleness, are difficult to process, contain heavy metal elements and radioactive elements, and have a large pollution to the environment, and the doped polymer-based persistent luminescent material has problems such as low solubility of the luminescent group in the polymer and uneven dispersion, so it is still a technical problem in the field to develop an easy-to-process and excellent luminescent performance intrinsic polymer-based persistent luminescent material. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application aims to provide a cyclic olefin copolymer and a preparation method and application thereof. The present application connects a chromophore and a polymer through a chemical bond to obtain an intrinsic polymer-based long afterglow material, which can solve the problems of low solubility and uneven dispersion of luminophores in the polymer and avoid phase separation, so that the polymer-based long afterglow material has more stable phosphorescent properties and optical properties. The cyclic olefin copolymer of the present application is more stable, has better optical properties and is easier to process, and can meet the current market use requirements.

[0007] To achieve this purpose, the present application adopts the following technical solutions:

[0008] In one aspect, the present application provides a cyclic olefin copolymer, the structure of which is shown in the following formula I:

[0009]

[0010] wherein R0 is independently selected from a pyrene group, a naphthalene group, a phenanthrene group, a naphthalimide group, a terphenyl group or an anthraquinone group; R1, R2, R3 and R4 are each independently selected from H, a halogen, a substituted or unsubstituted C1-C20 (e.g. C1, C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18 or C20) linear or branched alkyl group, a substituted or unsubstituted C3-C20 (e.g. C3, C4, C5, C6, C8, C10, C12, C14, C16, C18 or C20) cycloalkyl group, a substituted or unsubstituted C6-C30 (e.g. C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 or C30) aryl group, a substituted or unsubstituted C3-C20 (e.g. C3, C4, C5, C6, C8, C10, C12, C14, C16, C18 or C20) heteroaryl group, and R is selected from hydrogen or a C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) alkyl group; a is 0, 1 or 2; b is 0 or 1, x+y+z=100%, x is 1-15% (e.g. 1%, 3%, 5%, 8%, 10%, 12% or 15%), y is 55-99% (e.g. 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95% or 99%), and z is 0-30% (e.g. 0%, 1%, 5%, 10%, 15%, 20%, 25% or 30%).

[0011] Preferably, the weight average molecular weight of the cyclic olefin copolymer is 5000-400000, e.g. 5000, 8000, 10000, 30000, 50000, 80000, 100000, 200000, 300000 or 400000.

[0012] Preferably, the polymerized monomers of the cyclic olefin copolymer comprise an alpha-olefin, a cyclic olefin monomer having the structure of Formula II, and optionally a cyclic olefin monomer having the structure of Formula III;

[0013] 、 ;

[0014] wherein R0is independently selected from a pyrene group, a naphthalene group, a phenanthrene group, a naphthalimide group, a terphenyl group, or an anthraquinone group; R1, R2, R3, R4are each independently selected from H, a halogen, a substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C20) linear or branched alkyl group, a substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C20) cyclic alkyl group, a substituted or unsubstituted C6-C30 (e.g., C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, or C30) aryl group, a substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C20) heteroaryl group; a is 0, 1, 2; b is 0 or 1.

[0015] The method of the present application for preparing the intrinsic polymer-based long afterglow material by chemically linking the chromophore to the polymer to prepare the polymer-based long afterglow material compared to the doped polymer-based long afterglow system can solve the problems of low solubility of the luminophore in the polymer, uneven dispersion, etc. and avoid phase separation, so that the prepared polymer-based long afterglow material has more stable phosphorescent properties and optical properties. The intrinsic polymer-based long afterglow material is more stable, has better optical properties, and is easier to process, which can meet the current market use requirements.

[0016] Preferably, the alpha-olefin is selected from any one of ethylene, propylene, butylene, or pentene, preferably ethylene or butylene.

[0017] Preferably, the R0is selected from a pyrene group, a naphthalene group, a phenanthrene group, or a terphenyl group.

[0018] Preferably, the cyclic olefin monomer having the structure of Formula II is selected from any one of the following compounds IIa-II d:

[0019] .

[0020] Preferably, the R1, R2, R3, R4are each independently selected from H, a C1-C5 alkyl group, a C3-C6 cyclic alkyl group, or a C6-C8 aryl group.

[0021] Preferably, the compound having Formula III is selected from any one of the following compounds IIIa~IIId:

[0022] .

[0023] In another aspect, the present application provides a method for preparing the cyclic olefin copolymer as described above, the method comprising the following steps:

[0024] polymerizing the compound having Formula II, optionally the compound having Formula III, and the α-olefin to obtain the cyclic olefin copolymer.

[0025] Preferably, the molar ratio of the compound having Formula II, the compound having Formula III, and the α-olefin is x:y:z = (1~15%):(55~99%):(0~30%). Wherein x is 1~15%, for example 1%, 3%, 5%, 8%, 10%, 12% or 15%, y is 55~99%, for example 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95% or 99%, and z is 0~30%, for example 0%, 1%, 5%, 10%, 15%, 20%, 25% or 30%.

[0026] Preferably, the polymerization is catalyzed by a catalyst, the catalyst comprising a main catalyst and a co-catalyst, the main catalyst being a metallocene catalyst, and the co-catalyst being an alkyl aluminum co-catalyst or an organic boron compound.

[0027] Preferably, the metallocene catalyst is a metallocene compound of transition metal such as titanium, zirconium, hafnium, etc., including but not limited to Cp2TiCl2, (Flu)2SiE2TiCl2, (H4Ind)2SiMe2TiBr2, (4-MeInd)2SiMe2TiCl2, (2,3-Me2Ind)2SiMe2TiCl2, (4,7-Me2Ind)2SiMe2TiCl2, (4,7-(OMe)2Ind)2SiMe2TiCl2, (H2Ind)2SiMe2TiCl2, (H2Ind)2SiMe2TiEt2(OEt), Cp2ZrCl2, (Ind)2ZrCl2, EtCp(Ind)ZrCl2, (Ind)2SiMe2Zr(Me)Cl, Cp2SiMe2ZrCl2, (Ind)2SiMe2ZrCl2, (Ind)2SiMe2Zr(H)(Cl), (Flu)2SiMe2ZrPh2, Me2Si(Ind)2HfCl2, Me2SiCp2HfCl2, (Flu)2SiMe2ZrCl 2、 Ph2Cp(Ind)HfCl 2、one or a combination of at least two of Cp2ZrCl2, (Ind)2ZrCl2, or Me2SiCp2HfCl2.

[0028] Preferably, the metallocene catalyst is in a molar ratio of 1 : (10 2 ~10 4 , for example 1 : 10 2 , 1 : 3 x 10 2 , 1 : 5 x 10 2 , 1 : 8 x 10 2 , 1 : 10 3 , 1 : 3 x 10 3 , 1 : 5 x 10 3 , 1 : 8 x 10 3 , or 1 : 10 4 , further preferably 1 : (10 2 ~10 3 ).

[0029] Preferably, the alkylaluminum cocatalyst is at least one of a trialkylaluminum or an alkylaluminoxane (MAO), including but not limited to any one or a combination of at least two of trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t-butylaluminum, triamylaluminum, trihexylaluminum, trioctylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride, methylaluminoxane, ethylaluminoxane, methyldiethylaluminoxane, ethyldiethylaluminoxane, phenoxydiethylaluminoxane, modified methylaluminoxane (MMAO), preferably triethylaluminum or methylaluminoxane (MAO).

[0030] Preferably, the organoboron compound is selected from one or a combination of at least two of cyclo-boroxane, triethylborane, triphenylborane, triphenylborane ammine complex, sodium borohydride, tributyl borate, triisopropyl borate, tris(pentafluorophenyl)borane, diethylphenylammonium tetrakis(pentafluorophenyl)borate, methyldiphenylammonium tetrakis(pentafluorophenyl)borate, ethyldiphenylammonium tetrakis(pentafluorophenyl)borate.

[0031] Preferably, the polymerization reaction is carried out in the presence of a chain transfer agent, which is any one or a combination of at least two of hydrogen, dimethyl zinc, diethyl zinc, dipropyl zinc or diisobutyl zinc. Preferably, it is dimethyl zinc.

[0032] Preferably, the molar ratio of the chain transfer agent to the metallocene catalyst is (5-1000):1, such as 5:1, 8:1, 10:1, 20:1, 30:1, 50:1, 80:1, 100:1, 150:1, 180:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1 or 1000:1, and further preferably (5-500):1.

[0033] Preferably, the polymerization reaction is carried out in an organic solvent selected from any one or a combination of at least two of cycloalkanes or aromatic hydrocarbons.

[0034] Preferably, the organic solvent includes, but is not limited to, one or a combination of at least two of dichloromethane, toluene, o-xylene, m-xylene, p-xylene, mesitylene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane or cyclooctane, and preferably toluene or cyclohexane.

[0035] Preferably, the mass ratio of the total of the compound having the structure shown in Formula II and the compound having the structure shown in Formula III to the solvent is (10-30):(70-90), such as 10:90, 15:85, 18:92, 20:80, 23:77, 25:75, 28:72 or 30:70, and further preferably (10-15):(85-90).

[0036] Preferably, the water oxygen content in the system of the polymerization reaction is <1 ppm.

[0037] In another aspect, the present application provides an application of the cyclic olefin copolymer as described above in a micro-endoscope searchlight material, a biomedical material, a high-end anti-counterfeiting technology material, a radiation detection material or an optoelectronic device material.

[0038] Compared with the prior art, the present application has the following beneficial effects:

[0039] The cycloolefin copolymer provided by the application connects the chromophore and the polymer by a chemical bond to obtain an intrinsic polymer-based long afterglow material, has a colorful afterglow effect, can solve the problems of low solubility and uneven dispersion of the luminophore in the polymer, and avoids phase separation, so that the polymer-based long afterglow material has more stable phosphorescent properties. The cycloolefin copolymer is more stable and easier to process, and can meet the current market use requirements. The technology has wide application in the fields of biomedical and health such as biological imaging, endoscopic navigation, military and national defense, and emerging intelligent materials. DETAILED DESCRIPTION

[0040] The technical solutions of the application will be further described through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the application and should not be regarded as specific limitations on the application.

[0041] [Preparation Example 1]

[0042] A compound having a structure shown in Formula IIa, and the reaction formula is as follows:

[0043]

[0044] The preparation method of the cycloolefin monomer provided by the preparation example includes the following steps:

[0045] A mixture of 5-norbornene-2,3-dicarboxylic anhydride (1.64 g, 10.0 mmol), 1-aminopyrene (2.17 g, 10 mmol) and acetic acid (200 mL) is heated to reflux for 36 hours or more. After cooling to room temperature, the product is concentrated. Purification is performed by column chromatography (volume ratio of ethyl acetate / petroleum ether = 1:4) to obtain a green powder product with a yield of about 72%.

[0046] [Preparation Example 2]

[0047] A compound having a structure shown in Formula IIIc, and the reaction formula is as follows:

[0048]

[0049] The preparation method of the cycloolefin monomer provided by the preparation example includes the following steps:

[0050] (1) 0.5 mol of dicyclopentadiene (DCPD) and 0.001 mol of Ru-Al2O3 catalyst are subjected to selective hydrogenation at 50°C for 1.5 min to obtain 5,6-dihydrodicyclopentene (DCP);

[0051] (2) 0.5 mol 5,6-dihydrodicyclopentene and 0.1 mol dicyclopentadiene were reacted at 230°C for 90 min, and distilled under reduced pressure to obtain a cycloolefin monomer having a purity of more than 99%.

[0052] [Example 1]

[0053] This example provides a multi-color afterglow cycloolefin copolymer, and a preparation method thereof includes the following steps:

[0054] In a 2.5L reactor, the pressure was maintained at 20 bar, and the system was repeatedly vacuumed and replaced with nitrogen three times at 150°C, then replaced with ethylene three times, and the ethylene flow rate was maintained at 35 NL / hr to ensure that the entire reaction system was sealed, water-free and oxygen-free. The temperature of the system was set to 25°C;

[0055] Then 102.4g of the compound of formula IIa and 40.2g of the compound of formula IIIa, 1480ml of toluene, 7.35ml of dimethyl zinc were added to the system, and the catalyst used was ZrCp2Cl2, which was prepared into a solution with a concentration of 10μmol / L in toluene, and 70.81ml was taken. The cocatalyst was triethylaluminum, which was prepared into a solution with a concentration of 5mol / L in toluene, and 84.97ml was taken. After 20min of reaction, 2ml of methanol was injected to terminate the reaction.

[0056] Then 2 / 5 of the polymer solution was added to a 10wt% NaOH aqueous solution, and the polymer solution was washed with pure water to neutralize the polymer solution, and the polymer was precipitated with three times more ethanol. The polymer was vacuum dried at 190°C for more than 2 hours to obtain 119.59g of polymer.

[0057] [Example 2]

[0058] This example provides a multi-color afterglow cycloolefin copolymer, which is different from Example 1 only in that 44.51g of the compound of formula IIa and 50g of the compound of formula IIIb are used, the catalyst used is ZrCp2Cl2, which is prepared into a solution with a concentration of 10μmol / L in toluene, and 41.05ml is taken. The cocatalyst is triethylaluminum, which is prepared into a solution with a concentration of 5mol / L in toluene, and 49.26ml is taken. 4.26ml of dimethyl zinc, 983ml of toluene, and the rest of the conditions are the same as in Example 1. After polymerization and treatment, 80.33g of polymer was obtained.

[0059] [Example 3]

[0060] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 76.49 g of the compound of Formula Ila and 60 g of the compound of Formula lie are used, the catalyst used is ZrCp2Cl2, a solution of which is prepared in toluene at a concentration of 10 μmol / L, 52.91 ml is taken, the co-catalyst is triethylaluminum, a solution of which is prepared in toluene at a concentration of 5 mol / L, 63.49 ml is taken, 5.49 ml of dimethylzinc, 1418 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 88.72 g of polymer is obtained.

[0061] [Example 4]

[0062] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 54.01 g of the compound of Formula Ila and 40 g of the compound of Formula HID are used, the catalyst used is ZrCp2Cl2, a solution of which is prepared in toluene at a concentration of 10 μmol / L, 33.21 ml is taken, the co-catalyst is triethylaluminum, a solution of which is prepared in toluene at a concentration of 5 mol / L, 39.85 ml is taken, 3.45 ml of dimethylzinc, 977.01 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 82.73 g of polymer is obtained.

[0063] [Example 5]

[0064] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 52.68 g of the compound of Formula lib and 40 g of the compound of Formula Ilia are used, the catalyst used is ZrCp2Cl2, a solution of which is prepared in toluene at a concentration of 10 μmol / L, 60.69 ml is taken, the co-catalyst is triethylaluminum, a solution of which is prepared in toluene at a concentration of 5 mol / L, 72.83 ml is taken, 6.30 ml of dimethylzinc, 963.20 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 82.49 g of polymer is obtained.

[0065] [Example 6]

[0066] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 20.79 g of the compound of Formula lib and 50 g of the compound of Formula Illb are used, the catalyst used is ZrCp2Cl2, a solution of which is prepared in toluene at a concentration of 10 μmol / L, 35.92 ml is taken, the co-catalyst is triethylaluminum, a solution of which is prepared in toluene at a concentration of 5 mol / L, 43.10 ml is taken, 3.73 ml of dimethylzinc, 735.64 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 61.58 g of polymer is obtained.

[0067] [Example 7]

[0068] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 39.36 g of the compound of Formula IIb and 60 g of the compound of IIIc are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 45.35 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 54.12 ml is taken, 4.71 ml of dimethylzinc, 1032.66 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 81.48 g of polymer is obtained.

[0069] [Example 8]

[0070] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 44.04 g of the compound of Formula IIb and 50 g of the compound of IIId are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 38.05 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 45.66 ml is taken, 3.95 ml of dimethylzinc, 977.30 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 81.81 g of polymer is obtained.

[0071] [Example 9]

[0072] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 84.68 g of the compound of Formula IIc and 40 g of the compound of IIIa are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 67.44 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 80.92 ml is taken, 7.00 ml of dimethylzinc, 1295.79 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 74.81 g of polymer is obtained.

[0073] [Example 10]

[0074] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 19.51 g of the compound of Formula IIc and 40 g of the compound of IIIb are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 28.74 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 34.48 ml is taken, 2.98 ml of dimethylzinc, 618.41 ml of toluene, and the remaining conditions are the same as in Example 1. After polymerization and post-processing, 52.36 g of polymer is obtained.

[0075] [Example 11]

[0076] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 18.48 g of the compound of Formula IId and 40 g of the compound of IIIa are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 47.21 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 56.65 ml is taken, 4.90 ml of dimethylzinc, 607.75 ml of toluene, and the rest of the conditions are the same as in Example 1. After polymerization and post-processing, 52.36 g of polymer is obtained.

[0077] [Example 12]

[0078] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 10.00 g of the compound of Formula IId and 40 g of the compound of IIIc are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 25.54 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 30.65 ml is taken, 2.65 ml of dimethylzinc, 519.62 ml of toluene, and the rest of the conditions are the same as in Example 1. After polymerization and post-processing, 42.50 g of polymer is obtained.

[0079] [Example 13]

[0080] This example provides a multi-color afterglow cyclo-olefin copolymer, which differs from Example 1 only in that 40 g of the compound of Formula IIa is used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 11.06 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 13.28 ml is taken, 2.21 ml of dimethylzinc, 415.70 ml of toluene, and the rest of the conditions are the same as in Example 1. After polymerization and post-processing, 16 g of copolymer is obtained.

[0081] [Comparative Example 1]

[0082] Unlike Example 1, 20 g of the compound of Formula IIIa and 20 g of the compound of Formula IIIb are used, the catalyst used is ZrCp2Cl2, a solution of 10 μmol / L is prepared using toluene, 32.73 ml is taken, the co-catalyst is triethylaluminum, a solution of 5 mol / L is prepared using toluene, 39.28 ml is taken, 6.54 ml of dimethylzinc, 415.70 ml of toluene, and the rest of the conditions are the same as in Example 1. After polymerization and post-processing, 32.00 g of copolymer is obtained.

[0083] [Comparative Example 2]

[0084] Different from example 1, 40g of formula IIIa was used, the catalyst used was ZrCp2Cl2, 22.98ml of which was prepared into a 10μmol / L solution with toluene, the co-catalyst was triethylaluminum, 27.58ml of which was prepared into a 5mol / L solution with toluene, 4.59ml of dimethylzinc, 415.70ml of toluene, the rest of the conditions were the same as example 1. After polymerization and post-processing, 29.20g of copolymer was obtained.

[0085] [Comparative Example 3]

[0086] Different from example 2, 40g of formula IIIb was used, the catalyst used was ZrCp2Cl2, 22.98ml of which was prepared into a 10μmol / L solution with toluene, the co-catalyst was triethylaluminum, 27.58ml of which was prepared into a 5mol / L solution with toluene, 4.59ml of dimethylzinc, 415.70ml of toluene, the rest of the conditions were the same as example 1. After polymerization and post-processing, 29.20g of copolymer was obtained.

[0087] [Comparative Example 4]

[0088] The polymer obtained in comparative example 1 was dissolved in dichloromethane, 1wt% of IIa dichloromethane solution was added, magnetic stirring was used to stir for 4h, and then more than three times of ethanol was used to precipitate, to obtain a doped polymer-based long afterglow polymer.

[0089] The cycloolefin copolymers obtained in the above examples and comparative examples were subjected to the following performance characterization, and the relevant test results are summarized in Table 1:

[0090] (1) Film preparation: 0.5g of the prepared polymer was fully dissolved in 10mL of toluene, the polymer solution was slowly and uniformly dropped on a quartz sheet, and the quartz sheet was placed in a vacuum oven at 75℃ to ensure that the solvent was completely removed, to obtain a complete and transparent film for photophysical performance test.

[0091] (2) x, y, z: The structure of the prepared polymer was determined using a nuclear magnetic resonance spectrometer (NMR, Bruker 400MHz, Bruker, Switzerland) at 25℃, with deuterated chloroform (CDCl3) as the solvent and tetramethylsilane (TMS) as the internal standard.

[0092] (3) Glass transition temperature (Tg): tested by using a differential scanning calorimeter (Discovery 25, TA Instruments), taking 5.0-7.0 mg of polymer sample, heating to 260°C at a rate of 40°C / min, keeping constant for 5 min to eliminate thermal history, then cooling to 40°C at a rate of 20°C / min, keeping constant for 5 min, and then heating to 260°C at a rate of 20°C / min, obtaining the glass transition temperature of the polymer from the second heating curve;

[0093] (4) Molecular weight (Mw): determined by GPC-IR high-temperature gel permeation chromatography (Polymer Char); taking 8.0 mg of polymer sample in a 10 ml headspace bottle, adding 8 ml of 1,2,4-trichlorobenzene, and shaking to dissolve within 60 min; if the sample is completely dissolved, the sample is automatically injected after sequencing, and the molecular weight can be obtained from the injection curve.

[0094] (5) Afterglow color and afterglow time: using a 365 nm ultraviolet lamp (LUYOR-3405A, Shanghai Luyang Biotechnology Co., Ltd.) to irradiate the prepared polymer film for 30 s, and taking a digital camera to take a picture of the afterglow of the film after irradiation;

[0095] (6) Phosphorescence lifetime: after the polymer film is irradiated for 30 s using an ultraviolet lamp of different wavelengths, a phosphorescence spectrometer (FLS1000, Edinburgh Instruments) is used to excite the prepared polymer film under a light source of 365 nm, the phosphorescence intensity is monitored over time, and the phosphorescence lifetime is obtained by fitting an exponential curve;

[0096] (7) Haze: determined by a haze meter (HAM-300, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.), and the polymer is molded into a circular piece with a diameter of 25 mm and a thickness of 1 mm, and the haze is tested under a standard C light source of 380-780 nm;

[0097] (8) Light transmittance: determined by a double-beam ultraviolet-visible spectrophotometer (TU-19, Beijing Purui General Instrument Co., Ltd.), and the polymer is configured into a 1 mg / mL solution using toluene, and the light transmittance is tested under a standard C light source of 380 nm.

[0098] Table 1 Copolymer data table

[0099]

[0100] From the data in Table 1, it can be seen that:

[0101] The method for preparing the intrinsic polymer-based long afterglow material by copolymerizing the compound with formula II, the compound with formula III and α-olefin, connecting the chromophore and the polymer by chemical bond can solve the problems of low solubility of the luminophore in the polymer, uneven dispersion and the like, avoid phase separation, and make the prepared polymer-based long afterglow material have more stable phosphorescent performance and the same optical performance as the cyclic olefin copolymer;

[0102] When the compound with formula III is 0, the cyclic olefin copolymer obtained by copolymerization can also produce afterglow.

[0103] Compared with examples 1 and 2, the cyclic olefin copolymers provided by comparative examples 1 and 2 and comparative example 3 cannot produce afterglow.

[0104] Compared with example 1, the doped polymer of comparative example 4 can produce afterglow, but the optical performance of the polymer is reduced.

[0105] The cyclic olefin copolymer obtained by copolymerizing the compound with formula II, the compound with formula III and α-olefin can make the cyclic olefin copolymer produce afterglow of different colors.

[0106] The applicant declares that the cyclic olefin copolymer, the preparation method and the application thereof of the present application are illustrated by the above examples, but the present application is not limited to the above examples, that is, the present application does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes and the like all fall within the protection scope and the disclosed scope of the present application.

Claims

1. A cyclic olefin copolymer, characterized in that, The structure of the cyclic olefin copolymer is shown in Formula I below: ； Wherein, R0 is independently selected from pyrene, naphthyl, phenanthrene, naphthalimide, terphenyl, or anthraquinone; R1, R2, R3, and R4 are each independently selected from H, halogen, substituted or unsubstituted C1-C20 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C20 heteroaryl; R is selected from hydrogen or C1-C6 alkyl; a is 0, 1, or 2; b is 0 or 1; x+y+z=100%, x is 1~15%, y is 55~99%, and z is 0~30%; The weight-average molecular weight of the cyclic olefin copolymer is 5,000 to 400,000.

2. The cyclic olefin copolymer according to claim 1, characterized in that, The polymerizable monomers of the cyclic olefin copolymer include α-olefins, cyclic olefin monomers having the structure shown in Formula II, and optionally cyclic olefin monomers having the structure shown in Formula III. 、 ； Wherein, R0 is independently selected from pyrene, naphthyl, phenanthrene, naphthalimide, terphenyl, or anthraquinone; R1, R2, R3, and R4 are each independently selected from H, halogen, substituted or unsubstituted C1-C20 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C20 heteroaryl; a is 0, 1, or 2; b is 0 or 1; The α-olefin is selected from any one of ethylene, propylene, butene, or pentene.

3. The cyclic olefin copolymer according to claim 2, characterized in that, The R0 is selected from pyrene, naphthyl, phenanthrene, or terphenyl; R1, R2, R3, and R4 are each independently selected from H, C1-C5 alkyl groups, C3-C6 cycloalkyl groups, or C6-C8 aryl groups.

4. The cyclic olefin copolymer according to claim 2, characterized in that, Cycloolefin monomers having the structure shown in Formula II are selected from any one of the following compounds IIa to IId: ； The compound having Formula III is selected from any one of the following compounds IIIa to IIId: 。 5. The method for preparing the cyclic olefin copolymer according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: The cyclic olefin copolymer shown is obtained by polymerizing a compound of Formula II, or optionally a compound of Formula III, with an α-olefin.

6. The preparation method according to claim 5, characterized in that, The molar ratio of the compound of Formula II, the compound of Formula III, and the α-olefin is x:y:z = (1~15%):(55~99%):(0~30%). The polymerization reaction is carried out under the catalysis of a catalyst, which includes a main catalyst and a co-catalyst. The main catalyst is a metallocene catalyst, and the co-catalyst is an alkylaluminum co-catalyst or an organoboron compound. The metallocene catalyst is a metallocene compound of a transition metal, including titanium, zirconium, and hafnium. The molar ratio of the metallocene catalyst to the total number of compounds having the structure shown in Formula II and the structure shown in Formula III is 1:(10) 2 ~10 4 ); The alkylaluminum cocatalyst is at least one of trialkylaluminum or alkylaluminoxane.

7. The preparation method according to claim 6, characterized in that, The metallocene catalyst is Cp₂TiCl₂, (Flu)₂SiE₂TiCl₂, (H₄Ind)₂SiMe₂TiBr₂, (4-MeInd)₂SiMe₂TiCl₂, (2,3-Me₂Ind)₂SiMe₂TiCl₂, (4,7-Me₂Ind)₂SiMe₂TiCl₂, (4,7-(OMe)₂Ind)₂SiMe₂TiCl₂, (H₂Ind)₂SiMe₂TiCl₂, (H₂Ind)₂SiMe₂ TiEt2(OEt), Cp2ZrCl2, (Ind)2ZrCl2, EtCp(Ind)ZrCl2, (Ind)2SiMe2Zr(Me)Cl, Cp2SiMe2ZrCl2, (Ind)2SiMe 2ZrCl2, (Ind)2SiMe2Zr(H)(Cl), (Flu)2SiMe2ZrPh2, Me2Si(Ind)2HfCl2, Me2SiCp2HfCl2, (Flu)2SiMe2ZrCl 2、 Ph2Cp(Ind)HfCl 2、 One or a combination of at least two of the following: (Ind)2SiMe2Hf(OEt)Cl, (Ind)2SiMe2HfMe2, (Ind)2SiMe2HfEt2, (Ind)2SiMe2Hf(Bn)2, (Ind)2SiMe2HfMeBr, (Ind)2SiMe2Hf(Bn)Cl, (Ind)2SiMe2Hf(Me)Cl, (Flu)2SiMe2HfMe2, (Flu)2SiMe2HfPh2, and Ph2Cp(Flu)HfCl2; The alkylaluminum cocatalyst is selected from any one or a combination of at least two of the following: trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, methylaluminoxane, ethylaluminoxane, methoxydimethylaluminum, ethoxydiethylaluminum, and phenoxydiethylaluminum. The organoboron compound is selected from one or a combination of at least two of the following: cycloboroxane, triethylborane, triphenylborane, triphenylborane amino complex, sodium borohydride, tributyl borate, triisopropyl borate, tri(pentafluorophenyl)borane, diethylphenylammonium tetra(pentafluorophenyl)borate, methyldiphenylammonium tetra(pentafluorophenyl)borate, and ethyldiphenylammonium tetra(pentafluorophenyl)borate.

8. The preparation method according to claim 5, characterized in that, The polymerization reaction is carried out under the catalysis of a catalyst, which includes a main catalyst and a co-catalyst. The main catalyst is a metallocene catalyst, and the co-catalyst is any one or a combination of at least two of dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride, or modified methylaluminoxane.

9. The preparation method according to claim 6, characterized in that, The polymerization reaction is carried out in the presence of a chain transfer agent, which is any one or a combination of at least two of hydrogen, dimethyl zinc, diethyl zinc, dipropyl zinc, or diisobutyl zinc, and the molar ratio of the chain transfer agent to the metallocene catalyst is (5~1000):

1. The polymerization reaction is carried out in an organic solvent selected from any one or a combination of at least two of cycloalkanes or aromatics, and the mass ratio of the sum of the compounds having the structure shown in Formula II and the compounds having the structure shown in Formula III to the organic solvent is (10~30):(70~90). The water and oxygen content in the polymerization system is <1 ppm.

10. The application of the cyclic olefin copolymer according to any one of claims 1-4 in the preparation of materials for micro-endoscope searchlights, biomedical materials, high-end anti-counterfeiting technology materials, radiation detection materials, or optoelectronic equipment materials.

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